Polymerization process using metallocene complexes in the catalyst system

Abstract

A process for polymerizing C 2 -C 10 -alk-1-enes in the presence of a metallocene complex of the formula I ##STR1## where the substituent groups have the meanings described in the specification.

We claim: 
     
       1. A process for the preparation of a polymer of C 2  -C 10  -alk-1-enes which comprises: polymerizing the alk-1-ene at from 0.5 to 3000 bar and from -50° to 300° C. in the presence of a catalyst system, wherein the catalyst system comprises a metallocene complex of the formula I ##STR18## where M is titanium, zirconium, hafnium, vanadium, niobium or tantalum, X is fluorine, chlorine, bromine, iodine, hydrogen, C 1  -C 10  -alkyl, C 6  -C 15  -aryl or --OR 5 ,   R 5  is C 1  -C 10  -alkyl, C 6  -C 15  -aryl, C 1  -C 10  -alkylaryl, aryl C 1  -C 10  -alkyl, fluoro C 1  -C 10  -alkyl or fluoroaryl, where each aryl radical is of 6 to 20 carbon atoms,   R 1  to R 3  and   R 6  to R 8  are each hydrogen, C 1  -C 10  -alkyl or 5-membered to 7-membered cycloalkyl which in turn may carry C 1  -C 10  -alkyl substituents, or are each C 6  -C 15  -aryl or arylalkyl, where two neighboring radicals together may furthermore be a cyclic group of 4 to 15 carbon atoms, or Si(R 10 ) 3 ,   R 10  is C 1  -C 10  -alkyl, C 6  -C 15  -aryl or C 3  -C 10  -cycloalkyl,   R 4  is ##STR19## Q 1  is nitrogen, phosphorus, arsenic, antimony or bismuth, R 11  and R 12  are each C 1  -C 10  -alkyl, C 3  -C 15  -cycloalkyl, C 6  -C 15  -aryl, C 1  -C 10  -alkylaryl, aryl C 1  -C 10  -alkyl, fluoroalkyl or fluoroaryl, where each aryl radical is of 6 to 20 carbon atoms, or the two radicals R 11 , R 12  together may be a cyclic group of 2 to 15 carbon atoms which in turn may contain from 1 to 8 heteroatoms of main groups III to VI of the Periodic Table of Elements,   R 9  is hydrogen, C 1  -C 10  -alkyl or 5-membered to 7-membered cycloalkyl which in turn may carry C 1  -C 10  -alkyl substituents, or is C 6  -C 15  -aryl or arylalkyl, where two neighboring radicals together may furthermore by a cyclic group of 4 to 15 carbon atoms, or   Si(R 13 ) 3  or ##STR20## R 13  is C 1  -C 10  -alkyl, Q 2  is nitrogen, phosphorus, arsenic, antimony or bismuth,   R 14  and R 15  are each C 1  -C 10  -alkyl, C 3  -C 15  -cycloalkyl, C 6  -C 15  -aryl, C 1  -C 10  -alkylaryl, aryl C 1  -C 10  -alkyl, fluoroalkyl or fluoroaryl, where each aryl radical is of 6 to 20 carbon atoms, or the two radicals R 14 , R 15  together may be a cyclic group of 2 to 15 carbon atoms which in turn may contain 1 to 8 heteroatoms of main groups III to VI of the Periodic Table of Elements,   Y is ##STR21## Z is silicon, germanium, tin or carbon, and R 16 , R 17 , R 18  and R 19  are each hydrogen, C 1  -C 10  -alkyl, C 3  -C 10  -cycloalkyl or C 6  -C 15  -aryl, where two neighboring radicals together may furthermore be a cyclic group of 4 to 15 carbon atoms,   wherein said metallocene complex of the formula I when ##STR22## is reacted with a quaternizing agent of the formula V   A.sub.a X.sup.2                                            V       wherein   A is C 1  -C 10  -alkyl, C 3  -C 15  -cycloalkyl, C 6  -C 15  -aryl, C 1  -C 10  -alkylaryl, aryl C 1  -C 10  -alkyl, fluoro C 1  -C 10  -alkyl or fluoroaryl, where each aryl radical is of 6 to 20 carbon atoms,   X 2  is fluorine, chlorine, bromine, iodine, SO 3   2- , SO 4   2-   or NO 3- , and   a is 1 or 2,   and, the obtained product is optionally reacted with an open-chain or cyclic alumoxane compound of the formula VI or VII ##STR23## where R 20  is C 1  -C 4  -alkyl and   m is an integer from 5 to 30.